CN116850956A - Modified ZIF-8-based nitrogen-doped carbon CO 2 Method for preparing adsorbent - Google Patents
Modified ZIF-8-based nitrogen-doped carbon CO 2 Method for preparing adsorbent Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical class [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003463 adsorbent Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000005576 amination reaction Methods 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000006228 supernatant Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 230000008929 regeneration Effects 0.000 abstract description 8
- 238000011069 regeneration method Methods 0.000 abstract description 8
- 238000003795 desorption Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- -1 Zeolite imidazole ester Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JWDCJCRGZTUWDY-UHFFFAOYSA-N ethanol;3-trimethoxysilylpropan-1-amine Chemical compound CCO.CO[Si](OC)(OC)CCCN JWDCJCRGZTUWDY-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a modified ZIF-8-based nitrogen-doped carbon CO 2 The preparation method of the adsorbent solves the problem that the existing ZIF-8-based nitrogen-doped carbon has the effect of absorbing CO in the air 2 The adsorption and desorption capacity is weaker, the regeneration capacity is poor, and the use cost is higher. The method comprises the following steps: 1) Dissolving 2-methylimidazole in methanol to obtain a solution A, and dissolving zinc nitrate hexahydrate in methanol to obtain a solution B; 2) Adding the solution B into the solution A under the condition of stirring at room temperature, continuously stirring for reaction, centrifuging, washing to obtain clear supernatant after the reaction is finished, and vacuum drying to obtain ZIF-8; 3) Will step by stepCarbonizing the ZIF-8 obtained in the step 2), cooling to room temperature, removing impurities, washing and drying to obtain nitrogen-doped carbon; 4) Dispersing the nitrogen-doped carbon obtained in the step 3) in an amination grafting solution for reaction, and washing and drying after the reaction to obtain aminated nitrogen-doped carbon; 5) Introducing CO into the aminated nitrogen-doped carbon obtained in the step 4) 3 2‑ Vacuum drying to obtain modified ZIF-8-based nitrogen-doped carbon CO 2 An adsorbent.
Description
Technical Field
The invention belongs to the technical field of adsorbent synthesis, and in particular relates to a modified ZIF-8-based nitrogen-doped carbon CO 2 A preparation method of the adsorbent.
Background
Although a large amount of new energy is gradually developed and utilized, the use of fossil fuels still occupies a large proportion, which results in an increasingly serious greenhouse effect and thus reduces CO 2 The emission in the atmosphere is unprecedented. Therefore, a method capable of adsorbing CO at normal temperature and normal pressure is designed 2 The adsorbent of (2) can effectively reduce CO in the atmosphere 2 Has certain application value for environmental protection.
Existing CO 2 The air trapping adsorbent mainly comprises the following components: organic amines, hydroxides, basic salts, activated carbon, zeolites, metal Organic Frameworks (MOFs) materials, and the like. Among these adsorbents, activated carbon stands out for its extremely low cost, high ease of pore structure modification and surface functionalization, ease of regeneration, and high specific surface area. Zeolite imidazole ester framework (ZIF) materials are a large class of MOFs materials, and are receiving great attention in the field of gas adsorption due to their high specific surface area, high porosity and regular pore structure. However, ZIFs are quite sensitive to heat, humidity and chemicals, which limits their practical use.
ZIFs have the advantages of large specific surface area, large pore volume, high carbon content, pre-modified functional groups and the like, and have proved to be a promising hard template material for constructing microporous carbon in recent years. The ZIF-8-based nitrogen-doped carbon has a simple synthesis process, can obtain a high specific surface area through simple pyrolysis, and has high microporosity, so that the ZIF-8-based nitrogen-doped carbon is the most widely applied type of ZIFs-derived carbon; however, the existing ZIF-8-based nitrogen-doped carbon is used as an adsorbent for CO 2 The adsorption and desorption of the catalyst are all required to be carried out under higher pressure, and the required CO is 2 Higher concentration of (2) and thus for CO in air 2 Has weaker adsorption and desorption capability, poor regeneration capability and low use costHigher.
In view of this, there is a need for improvements over existing ZIF-8 based nitrogen-doped carbons.
Disclosure of Invention
The invention aims to solve the problem that the existing ZIF-8-based nitrogen-doped carbon has the effect of reducing CO in air 2 The adsorption and desorption capability is weaker, the regeneration capability is poor, and the use cost is higher, thereby providing the modified ZIF-8-based nitrogen-doped carbon CO 2 Method for preparing adsorbent, thereby obtaining CO absorption during drying 2 CO release upon wetting 2 For CO in air 2 Is included in the collection of the liquid.
In order to achieve the above purpose, the technical solution provided by the present invention is:
modified ZIF-8-based nitrogen-doped carbon CO 2 The preparation method of the adsorbent is characterized by comprising the following steps:
1) 2-methylimidazole (ml M) is dissolved in methanol to obtain a solution A, and zinc nitrate hexahydrate is dissolved in methanol (methanol is adopted, and the solution appearance is better) to obtain a solution B;
2) Slowly adding (dropping or injecting) the solution B into the solution A under the condition of stirring at room temperature, continuously and slowly stirring to perform full reaction, centrifuging and washing to obtain clear supernatant after the reaction is finished, and vacuum drying to obtain ZIF-8, namely preparing ZIF-8 by a solvent diffusion method;
3) Carbonizing the ZIF-8 obtained in the step 2), cooling to room temperature, removing impurities, washing and drying to obtain nitrogen-doped carbon;
4) Dispersing the nitrogen-doped carbon obtained in the step 3) in an amination grafting solution for reaction, washing and drying after the reaction to obtain aminated nitrogen-doped carbon, namely aminated porous carbon, wherein the pH value of a grafting reaction system is 10-11, and the mass fraction and the dosage of the amination grafting solution are controlled;
5) Introducing CO on the surface of the aminated nitrogen-doped carbon obtained in the step 4) 3 2- Vacuum drying to obtain modified ZIF-8-based nitrogen-doped carbon CO 2 The adsorbent can be uniformly mixed with the solid by grinding for a small amount of liquid.
The main mechanism of the wet adsorption of the invention is as follows:
the water on the surface of the adsorbent is dissociated during drying and reacts with carbonic acid radical to generate bicarbonate HCO 3 - With hydroxide radical HO - Hydroxyl radical and CO in air 2 Generating bicarbonate radical by reaction, namely generating CO 2 Is adsorbed by the adsorption column; bicarbonate reacts to form carbonate and hydroxide and release CO when wet 2 The specific reaction equation is as follows:
further, in the step 2), the molar ratio of the 2-methylimidazole to the zinc nitrate hexahydrate is 2-10:1.
Further, in the step 3), the carbonization refers to that ZIF-8 is placed in a tube furnace inert atmosphere and carbonized for 2-4 hours at 800-1000 ℃ at a heating rate of 2-5 ℃/min; the boiling point of Zn in the ZIF-8 skeleton is 907 ℃, so sublimation can occur along with the rise of carbonization temperature, a large number of micropore structures are formed, and the microporosity is improved.
Further, in the step 3), the impurity removal means that residual metallic zinc and impurities are removed by stirring for 4-6 hours at 60-80 ℃ in hydrochloric acid solution with the molar concentration of 1-3M, and the whole impurity removal adopts an acid washing process, preferably hydrochloric acid solution with the molar concentration of 2M.
Further, in the step 4), the mass ratio of the nitrogen-doped carbon to the amination substances in the amination grafting solution is 1:15-35;
the amination grafting solution is a 3-aminopropyl trimethoxy silane solution with the mass fraction of 5-15%, a 3-aminopropyl triethoxy silane solution with the mass fraction of 5-15% or a mixed solution of the two;
the reaction temperature is 60-100 ℃, and the reaction time is 4-6h, preferably 80 ℃ and 5h.
Further, the step 5) specifically comprises: soaking the aminated nitrogen-doped carbon obtained in the step 4) in Na with the molar concentration of 0.75-1M 2 CO 3 Vacuum drying for at least 10h to obtain modified ZIF-8-based nitrogen-doped carbon CO 2 An adsorbent. I.e. through Na 2 CO 3 Solution introduction of CO 3 2- Of course, it is also possible to introduce by other soluble carbonates, such as: potassium carbonate.
Further, in step 2), methanol is used for washing, and vacuum drying is carried out at 60-100 ℃, preferably 100 ℃;
in step 3), washing with deionized water and drying at 60-100 ℃, preferably 80 ℃;
in step 4), washing with ethanol and drying at 60℃to 100℃preferably at 80 ℃.
Further, in order to reduce the production cost, in the step 3), the inert atmosphere is N 2 。
The invention provides a modified ZIF-8-based nitrogen-doped carbon CO 2 The adsorbent is characterized in that: the preparation method is adopted.
In view of the adsorption effect and the regeneration capability of the adsorbent, the invention also provides a method for preparing CO in air 2 The trapping system is characterized in that the modified ZIF-8-based nitrogen-doped carbon CO prepared by the method is used 2 An adsorbent.
The invention has the advantages that:
the invention obtains the specific surface area up to 1355m by utilizing ZIF-8 direct pyrolysis 2 The nitrogen doped carbon per gram is firstly grafted by amino groups, so that physical adsorption is changed into chemical adsorption, and the material is enhanced for CO in the air 2 Capturing the driving force of absorption, and introducing a certain amount of carbonate on the surface of the nitrogen-doped carbon to enable the modified nitrogen-doped carbon to be capable of drying air at normal temperature and normal pressureCO in (b) 2 Capturing and releasing CO when wet 2 Improving the CO in the air of the material 2 The adsorption and desorption circulation mode can realize normal temperature and normal pressure CO 2 The regeneration and utilization of the material under low concentration greatly improves the adsorption and desorption capacity and has strong regeneration capacity; the preparation method has the advantages of simple preparation process, easy control of reaction process, rich and easily obtained raw materials, reduced preparation and use costs, and contribution to mass production.
Drawings
FIG. 1 is a graph showing the CO obtained in example 5 of the present invention 2 SEM image of adsorbent.
FIG. 2 is a drawing showing the nitrogen adsorption stripping of the adsorbents obtained in examples 3 to 5 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and specific examples:
example 1
1) 10mmol of 2-methylimidazole (mL M) was dissolved in 50mL of methanol to obtain solution A, and another beaker was taken to dissolve 5mmol of zinc nitrate hexahydrate in 50mL of methanol to obtain solution B;
2) Slowly dripping or slowly injecting the solution B into the solution A under the condition of stirring at room temperature, slowly stirring at room temperature for full reaction, centrifuging to obtain white solid after the reaction is finished, washing with methanol to obtain supernatant, clarifying, and vacuum drying at 100 ℃ to obtain ZIF-8;
3) The ZIF-8 thus obtained was heated in a tube furnace under an inert atmosphere (N 2 ) Carbonizing at 800 deg.c at 5 deg.c/min for 2 hr, cooling to room temperature, stirring the obtained nitrogen doped carbon in hydrochloric acid solution of molar concentration of 2M at 60 deg.c for 6 hr to eliminate residual zinc metal and other impurity, suction filtering, washing with deionized water and drying at 80 deg.c to obtain nitrogen doped carbon;
4) Dispersing the obtained nitrogen-doped carbon material in a 3-aminopropyl trimethoxy silane ethanol solution with the mass fraction of 5%, reacting at 80 ℃ for 5 hours, washing with ethanol, and drying at 80 ℃ to obtain aminated nitrogen-doped carbon; wherein the mass ratio of the nitrogen-doped carbon to the amination substances in the amination grafting solution is 1:15;
5) Immersing the aminated nitrogen-doped carbon sample in Na with the molar concentration of 1M 2 CO 3 Solution is treated for 12 hours and vacuum drying is carried out for 48 hours to obtain modified ZIF-8 based nitrogen doped carbon CO 2 An adsorbent.
Examples 2-16 differ from example 1 in the individual process parameters, the specific parameters being shown in Table 1:
table 1 process parameters of examples 2-16
S Bet : specific surface area;
microporosity: representing the percentage of micropore volume to total pore volume.
FIG. 1 is a scanning electron microscope image of the adsorbent obtained in example 5, from which it can be seen that the synthesized adsorbent has a small particle size, on the order of several hundred nanometers. FIG. 2 is a graph showing the nitrogen adsorption and pore size distribution before modification of the adsorbent in examples 3-5, from which it can be seen that carbonization at 800-900℃has an obvious hysteresis, indicating a large number of mesoporous structures, facilitating amino and CO 3 2- The specific surface area of the adsorbent after carbonization at 1000 c is significantly reduced because the high temperature causes collapse of the mesoporous structure and a large number of microporous structures are generated due to sublimation of Zn ions, which is consistent with the pore size distribution in fig. 2. Compared with mesoporous structure, the mesoporous structure is more favorable for grafting amino and CO 3 2- Is attached to the substrate.
As can be seen from Table 1, the modified ZIF-8-based nitrogen-doped carbon prepared by the method and under the process conditions has better CO 2 Adsorption capacity, therefore, the modified ZIF-8-based nitrogen-doped carbon prepared by the method can be used as CO in air 2 The adsorbent of the trapping system can desorb CO when wet (namely under the action of water molecules) based on the adsorption and desorption mechanism of the invention 2 And the material regeneration is realized.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made without departing from the spirit and scope of the invention.
Claims (10)
1. Modified ZIF-8-based nitrogen-doped carbon CO 2 The preparation method of the adsorbent is characterized by comprising the following steps:
1) Dissolving 2-methylimidazole in methanol to obtain a solution A, and dissolving zinc nitrate hexahydrate in methanol to obtain a solution B;
2) Adding the solution B into the solution A under the condition of stirring at room temperature, continuously stirring for reaction, centrifuging, washing to obtain clear supernatant after the reaction is finished, and vacuum drying to obtain ZIF-8;
3) Carbonizing the ZIF-8 obtained in the step 2), cooling to room temperature, removing impurities, washing and drying to obtain nitrogen-doped carbon;
4) Dispersing the nitrogen-doped carbon obtained in the step 3) in an amination grafting solution for reaction, and washing and drying after the reaction to obtain aminated nitrogen-doped carbon, wherein the pH of a grafting reaction system is 10-11;
5) Introducing CO on the surface of the aminated nitrogen-doped carbon obtained in the step 4) 3 2- Vacuum drying to obtain modified ZIF-8-based nitrogen-doped carbon CO 2 An adsorbent.
2. The modified ZIF-8-based nitrogen-doped carbon CO of claim 1 2 The preparation method of the adsorbent is characterized by comprising the following steps:
in the step 2), the molar ratio of the 2-methylimidazole to the zinc nitrate hexahydrate is 2-10:1.
3. The modified ZIF-8-based nitrogen-doped carbon CO according to claim 1 or 2 2 The preparation method of the adsorbent is characterized by comprising the following steps:
in the step 3), the carbonization refers to the carbonization of ZIF-8 in a tube furnace inert atmosphere at the temperature rising rate of 2-5 ℃/min at 800-1000 ℃ for 2-4h.
4. The modified ZIF of claim 3-8-base nitrogen doped carbon CO 2 The preparation method of the adsorbent is characterized by comprising the following steps:
in the step 3), the impurity removal refers to the removal of residual metallic zinc and impurities by stirring in a hydrochloric acid solution with the molar concentration of 1-3M at the temperature of 60-80 ℃ for 4-6 hours.
5. The modified ZIF-8-based nitrogen-doped carbon CO of claim 4 2 The preparation method of the adsorbent is characterized by comprising the following steps:
in the step 4), the mass ratio of the nitrogen-doped carbon to the amination substances in the amination grafting solution is 1:15-35;
the amination grafting solution is a 3-aminopropyl trimethoxy silane solution with the mass fraction of 5-15%, a 3-aminopropyl triethoxy silane solution with the mass fraction of 5-15% or a mixed solution of the two;
the reaction temperature is 60-100 ℃ and the reaction time is 4-6h.
6. The modified ZIF-8-based nitrogen-doped carbon CO of claim 5 2 The preparation method of the adsorbent is characterized in that the step 5) is specifically as follows:
soaking the aminated nitrogen-doped carbon obtained in the step 4) in Na with the molar concentration of 0.75-1M 2 CO 3 Vacuum drying for at least 10h to obtain modified ZIF-8-based nitrogen-doped carbon CO 2 An adsorbent.
7. The modified ZIF-8-based nitrogen-doped carbon CO of claim 6 2 The preparation method of the adsorbent is characterized by comprising the following steps:
in the step 2), methanol is adopted for washing, and vacuum drying is carried out at the temperature of 60 ℃ to 100 ℃;
in the step 3), deionized water is adopted for washing, and the washing is dried at the temperature of 60 ℃ to 100 ℃;
in step 4), ethanol is used for washing and drying is carried out at 60-100 ℃.
8. The modified ZIF-8-based nitrogen-doped carbon CO of claim 6 2 The preparation method of the adsorbent is characterized by comprising the following steps:
step 3), the inert atmosphere is N 2 。
9. Modified ZIF-8-based nitrogen-doped carbon CO 2 The adsorbent is characterized in that: a method according to any one of claims 1 to 8.
10. CO in air 2 The trapping system is characterized in that: the modified ZIF-8-based nitrogen-doped carbon CO prepared by the method of any one of claims 1 to 8 is used in the trapping system 2 An adsorbent.
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